Herbicidal halophenoxy benzoic acid salts

ABSTRACT

Metal salts and amine salts of 2-nitro-5-(halophenoxy)benzoic acids comprise a class of compounds that are highly effective pre- and post-emergence herbicides.

Unlted States Patent 1 1 1 3,929,455

Theissen Dec. 30, 1975 [54] HERBICIDAL HALOPHENOXY BENZOIC 3,423,4701/1969 Rohr et a1 71 124 ACID SALTS 3,475,427 10/1969 Blank et al.....260/244 3,776,961 12/1973 Theissen 71/124 [75] I en o obe t J. e swestfield, NJ 3,798,276 3/1974 Bayer 71 124 [73] Assignee: Mobil OilCorporation, New York,

N.Y. Primary Examiner-Lewis Gotts Filedi p 12, 1973 AssistantExaminer--Catherine L. Mills 2 App] 396 30 Attorney, Agent, orFirmChar1es A. Huggett;

. Hastings S. Trigg Related U.S. Application Data [60]Continuation-impart of Ser. No. 194,479, Nov. 1, 1971, Pat. No.3,776,715, which is a division of Ser. No. 819,412, Aprll 25, 1969, Pat.No. 3,652,645. ABSTRACT [52] U.S. Cl. 71/115; 71/88; 71/92;

' 71/93; 7l/94; 5; 71/96 Metal salts and amme salts of2-n1tro-5-(halophenox- [51] Int. Cl. A01N 9/24 Whenzoic acids comprise aClass of compounds that [58] Field 01 Search 71/108, 115, 124 are highlyeffective p and post-emergence herbicides.

[56] References Cited 20 Claims, No Drawings HERBICIDAL HALOPHENOXYBENIZOIC ACID SALTS" I Cross-reference to Related Applications Thisapplication is a continuation-in-part of'copending application Ser. No.194,479, filed Nov; 1, 1971, now US. Pat. No. 3,776,7l which is adivision of application Ser. No. 819,412, filed April 25, 1969, now US.Pat. No. 3,652,645.

BACKGROUND OF THE INVENTION SUMMAllY OF THE INVENTION This inventionprovides the method for controlling plant growth that comprises applyingan herbicidal amount of an herbicidalcompound having the formula:

COOM

wherein X is halogen, n is 5, and M is alkali metal (Li, Na, K),alkaline earth.,metal (Ca, Mg, Ba, Sr), transition metal (e.g. Cu, Fe),ammonium, alkylampared from the halophenoxybenzoic acid, using wellknown. salt forming procedures.

The salts contemplated herein include metal salts, ammonium salts,and'amine salts. The metal salts are the alkali metal salts (Li, Na, K);alkaline earth metal salts (Ca, Mg, Ba, etc.); and transition metalsalts (Cu, Fe, etc.).

In addition to the salts of ammonia, the amine salts contemplatedinclude salts of primary amines, secondary amines, tertiary amines, arylamines, and heterocyclic amines. The primary amines can have 1-30 carbonatoms and can be saturated or unsaturated, straight chain, branchedchain, or cyclic. Non-limiting examples of primary amines aremethylamine; ethylamine;

n-propylamine; isopropylamine; n-butylamine; dodecylamine;triacontylamine; allylamine; 2- propynylamine; cyclohexylamine;propargylamine;

isobutylamine; sec-butylamine; 2-ethylhexylamine;cyclopropylmethylamine; t-butylamine; 1,1-dimethyl-2- propynylamine;l,1-diethyl-2-propynylamine; tallow amine (e.g. Armeen T); 2,2-dimethoxyethylamine; l-ethylnylcyclohexylamine and benzylamine.

The secondary amines can have 2-30 carbon atoms and can be saturated orunsaturated, straight chain, branched chain, or cyclic. Non-limitingexamples of secondary amines are dimethylamine, diethylamine,dibutylamine, dioctylamine, ditetradecylamine, diallylamine,di-2-hexenylamine, dicyclohexylamine, methylethylamine, methylcyclohexylamine, diisopropylamine, diisopentylamine, ethylcyclohexylamine, (3-

aminopropyl)alkenylamine wherein the alkenyl group monium (C -Calkanolammonium (C -C alkyl (C -C ,,)dialkanol(C,-C )ammonium,dioxyalkylene(C -C )alkyl(C,-C )-ammonium, dialkylammonium (C -Ctrialkylammonium (C -C alkoxyalkylammonium (C -C dialkoxyalkylammonium(C -C aminoalkylammonium (C C dialkylaminoalkylammonium (C -Calkenylammonium (C -C alkyl(C,C, )aminoalkyl(C,-C )ammonium,alkenyl(C,-C )aminoalkyl(C,-C,)-ammonium, alkynyl(C -C ,)ammonium,'dialkenylammonium (C -C cycloalkylammonium (C -C alkyl(C C)ammoniumalkyl(C,-C )ammonium, benzylammonium, anilinium, substitutedanilinium, guanidinium, or heterocyclicammonium (C -C and an herbicidalcomposition containing said compound.

DESCRIPTIONYOI'FY SPECIFIC. EMBQDIMENT The compounds of this inventionare readily prepared by the Ullmann ether synthesis reaction between thealkali metal (Na, K) salt of a halophenol and a has 16 to 18 carbonatoms; (3-aminopropyl)alkenyla mine wherein the alkenyl group has 18, 20and 22 carbon atoms; and dihydrogenated tallow amine (e.g. Armeen 2HT).

The tertiary amines can have 3-30 carbon atoms and can be saturated orunsaturated, straight chain, branched chain, or cyclic. Non-limitingexamples of tertiary amines are trimethylamine, dimethyl ethylamine,triethylamine, tributylar nine, trioctylamine, triallylamine,trii'sopentylamine, tricyclohexylamine, dimethyl octylamine,n-hexadecyldimethylamine (e.g. Armeen DM16D), n-octadecyldimethylamine(e.g. Armeen DM18D), methyl di-hydrogenated tallowamine (e.g. ArmeenM2HT), and methyl di-cocoamine (e.g. Armeen M2C).

Non-limiting examples of arylamines are aniline; 2-chloroaniline;3-chloroaniline; 4-chloroaniline; 2- methyl-4-chloroaniline;2,4-dichloroaniline; 3,4- dichloroaniline; 2,6-dichloro-4-nitroaniline;m-trifluoromethylaniline; isopropylaniline; p-methoxyaninline;N-methoxymethyl-Z,6-diethylaniline; a-naphthylamine;N-sec-butyl-4-t-butyl-2,6-dinitroaniline; 3- amino-2,5-dichlorobenzoicacid; N,N-dipropyl a, a, a-trifluoro-2,6-dinitro-p-toluidine; 4-bromo-3-chloroaniline;4(4-chlorophenoxy)aniline; N, N-diethyl-2,4-dinitro-6-trifluoromethyl-m-phenylenediamine;p-dimethylaminoaniline; ydiphenylamine; pbromoaniline;m-aminophenyl-t-butylcarbamate; ophenylenediamine; m-phenylenediamine;4-dimethylamino-3,S-dimethylpheno]; 4-(methylsulfonyl)-2,6-dinitro-N,N-dipropylaniline; 3,5-dinitro-N,N- dipropylsulfanilamide;N-sec-butyl-4-t-butyl-2,6-dinitroaniline; m-toluidine; p-toluidine;m-t-butylaniline; o-anisidine; p-anisidine; dimethylaniline;o-nitroaniline; p-nitroaniline; and 4,4'-oxydianiline.

Non-limiting examples of heterocyclic amines are 3-aminol ,2,4-triazole; 2-chloro-4-ethylamino-6-iso- 4-amino-6-t-butyl-3 methylthio)-l ,2 ,4-triazine- 5(4H )-one; 6- ethoxy-1,2-dihydro-2,2,4-trimethylquinoline; indole; hexahydr-ll-l-azepine;4-amino-5-' chloro-2-phenyl-3(2l-l)-pyridazinone; pyrrole;imidazolidine; isoquinoline; 2,4-lutidine; 2-methyl-5- ethylpyridine;Z-dimethyl aminopyridine; a-picoline; B-picoline; 'y-picoline;quinoline; and 4,4'-dipyridine.

Non-limiting examples of other salt-forming amino compounds contemplatedare 2-chloroethyl dimethylamine; diethanolamine; quanidine;dodecylguanidine; 3-(4-chloro-phenyl )-1 ,1 -dimethylurea;chlorophenyl)-1,l-dimethylurea; Fenuron; Tandex B- alanine; methylglycine; glycinamide; aminoacetonitrile; aminoethanthiol; aminoaceticacid; diethyl ethanolamine; diethylenetriamine; isopropanolamine;diisopropanolamine; triisopropanolamine; ethylenediamine;hexamethylenetetramine; hydrazine; phenothiazine; sulfanilic acid;tetraethylenepentamine; thiourea; urea; triethanolamine;triethylenetetramine; diethanol soyaamine (e.g. Ethomeen S-l2) anddidacaoxyethyene soyaamine (e.g. Ethomeen S-). 1

The following example illustrates the preparation of a typical compoundof this invention and demonstrates a method for product recovery. i

EXAMPLE 1 Methyl 2-nitro-5-(2',4',6'-trichlorophenoxy)benzoate.

A stirred solution of methyl 5-chloro-2-nitrobenzoate (17.0 g., 0.079mole) and the potassium salt of 2,4,6- trichlorophenol (18.6 g., 0.079mole) in dimethyl sulfoxide (100 ml.) was heated at 90 for 17 hours. Thecooled reaction mixture was diluted with water (500 ml.) and thenextracted with ether (3 X 100 ml.). The combined ether fractions werewashed with 10% sodium hydroxide solution (2 X ml.) and then with asatuated aqueous sodium chloride solution. The ether solution was dried(Na SO and the solvent evaporated to give a dark oil. Twocrystallizations (petroleum ether) gave 1.91 g. of a pale yellow solid,mp. l0ll03.".

Example 1 LR. (numol):c=o 1723, c-o 1240, and 1260 cm NMR (CDCl;,):methyl 3.91 ppm (3H), quartet 6.96 ppm (1H, J 2.5 and 8 c.p.s.'),doublet 7.05 ppm (ll-l, J 2.5 c.p.s.), broad singlet 7.05 ppm (2H), anddoublet 8.01 ppm (1H, J 8

c.p.s.). I

EXAMPLES 2 THROUGH 24 4 The ester of Example 1 was hydrolyzed to thecorresponding acid and; using known salt-forming methods,

salt compounds within the scope of this invention were prepared. 1

These compounds are identified below, wherein A I 4 7. arachidyl(90%)-behenyl(10%)aminopropylammonium A. i

8. arachidyl (90% )-behenyl( 10%)ammoniumpropylammonium bis-[ A].

9. isobutylammonium A. 10. n-butylammonium A. ll. methoxypropylammoniumA. 12. copper bis-[A].

2,Z-dimethoxyethylammonium A. t-butylammonium A. benzylammonium A.allylammonium A. diallylammonium A. ethanolammonium A.3-dimethylaminopropylammonium A. cyclohexylammonium A. dim-butylammoniumA. v 22. N,N-dimethyl-3?(4-methyl-3-cyclohexen-l-yl)- butylammonium A.

23. 4-[3-(4-methyl-3-cyclohexen-l-yl)butyl]morpholium A.

24. N,N-dimethyl-3,3-dimethyl-2-norbornylethylammonium A. i

29. calcium A. 30. n-propylammonium A. 31. 4(4'-aminophenoxy)aniliniumA. 32. 4(4-phenoxyammonium)anilinium A. 33. 2-propylammonium A. 34.ammonium A. g 35. diethanolammonium A. 36. triethanolammonium A.

methylammonium A. trimethylammonium A. isopropylammonium A.sec-butylammonium A. Z-dimethylaminopyridine A. piperidine A. morpholineA. ethylammonium A. diethylammonium A. triethylammonium A. rp-methoxyanilinium A. alkenyl(C -C gaminopropylammonium A. alkenyl(C, -C)aminopropylammonium A. o-methoxyanilinium A. m-methoxyaniliniurn A.m-toluidine A. p-toluidine A. guanidine A. anilinium A.di(cyclohexyl)ammonium A. 3,4-dichloroanilinium A. m-chloroanilinium A.p-chloroanilinium A. isopropanolammonium A. diisopropylammonium A. l l-dimethyl-Zpropynylammonium A. l,l-diethyl 2-propynylammonium A. lethynylcyclohexylammonium A. n-dodecylamino A. a=Armeen 12D 66.di(hydrogenated tallow)amine A. b=Armeen 67 n-hexadecyldimethylamine A.c=Armeen DM16D 68. n-octadecyldimethylamino" A. d=Armeen DM18D 1 69.methyl di(hydrogenated tallow)amine A. e=Armeen MZHT i 70. methyldi-cocoa'mine A. f-Armeen M2C diethanol soyaamine A. g=Ethomeen S-l2 72.di(decao1tyethylene)soyaamine' A. h=Ethomeen 4,4'-dipyridinium A.

. pyridinium A.

. triisopropanolammonium A. tallowamine A. i=Armeen T diethanolammoniumC.

. triethanolammonium C. p-methoxyanilinium C.

. ethanolammonium C.

. sodium C.

. ammonium C.

. cyclohexylarnmonium C. morpholine C. i

. o-methoxyanilinium C.

. diethanolammonium B.

. triethanolammonium B. p-methoxyanilinium B.

. cyclohexylammonium B. momrpholine B.

. o-methoxyanilinium B.

. diethanolammonium D.

. triethanolammonium D.

. p-methoxyanilinium D.

. ethanolammonium D.

. sodium D.

. ammonium D.

. cyclohexylammonium D.

99. morpholine D.

100. o-methoxyanilium D.

For comparison, a position isomer of the acids used to form the salts of-this invention was prepared, as described in U.S. Pat. No. 3,475,427.Salts of this isomeric acid were prepared by known salt-forming methods.These compounds are:

(25) 2-nitro-3-(2,4-dichlorophenoxy)benzoic acid.

(26) ethanolammonium 2-nitro-3-(2,4'-dichlorophenoxy )benzoate. I Y

. (27) n-propylammonium 2-nitro-3-(2',4-dichlorophenoxy )benzoate'.

' (28) potassium 2-nitro-3-(2,4'-dichlorophenoxy) benzoate.

' The compounds of this invention can be applied in various ways toachieve herbicidal action. They can be 1 applied per se, as solids or invaporized form, but are preferably applied as the toxiccomponents inpesticidal compositions of the compound and a carrier. Thesecompositions are preferably applied directly to the soil compounds ofthis invention are effective herbicides when applied in herbicidalamounts, i.e., at rates between about 0.2 pounds and about 10 pounds peracre.

I-IERBICIDAL EFFECTIVENESS Method of Propagating Test Species CrabgrassYellow foxtail grass Johnson grass Barnyard grass Digitaria sanguinalisSetaria glauca Sprgum Halepense Echinochloa crus-galli All crop and weedspecies are planted individually in 3 inch plastic pots containingpotting soil. Four seeds of each of corn, cotton, and snapbeans areseeded to a solid carriers include talc, bentonite, diatomaceous earth,pyrophyllite, fullers earth, gypsum, flours derived from cotton seedsand nut shells, and various 1 natural and synthetic clays having a pllnot exceeding about 9.5. Non-limiting examples of liquid carriers.

include water, organic solvents such as alcohols, ketones, amides andesters, mineral oils such as kerosene,

I light oils,'and medium oils and vegetable oils such as depth equal tothe diameter of the seed. All other species are surface seeded andsprinkled with screened soil in an amount sufficient to cover the seeds.Immediately after planting, all pots are watered by sub-irrigation ingreenhouse trays. Pots for the pre-emergence phase are seeded one daybefore treatment.

Planting dates for the post-emergence phase are varied so that allthe'seedlings will reach the desired stage of developmentssimultaneously. The proper stage of seedling development for treatmentin the postemergence phase is as follows:

GRASSES: 2 inches in height PIGWEED, BINDWEED, l or 2 true leavesvisible VELVET LEAF & TURNIPS: above cotyledons COTTON: first true leaf1 inch in length; expanded cotyledons CORN: 3 inches-4 inches in heightBEANS: primary leaves expanded;

growing point at primary leaf node. 1

Method of Treatment Spray applications are made in a hood containing amovable belt and fixed spray nozzle. For passage through the spray hood,one pot of each species (preemergence phase) is placed on the forwardhalf of a wooden flat and one pot of established plants (postemergencephase) is placed onthe rear half of the flat. Treatments are movedto.the greenhouse after. spraying. Watering during the observationperiod is applied only by subirrigation. j

Compounds are screened initially at a rate of application equivalent tofour to eight pounds per acre. Two weeks after treatment the pre andpost-emergence percent injury is visually rated. Subsequent testing canbe carried out at 2,1 and 0.5 pounds per acre.

Herbicidal testing of the compounds of Examples 2 through 24 and 30through and the isomeric compounds showed the results set forth in TableI. The plants are tabulated using the following abbreviations:

Crabgrass CG Yellow foxtail YF grass Johnson grass 10 Barnyard grass BGPigweed PW monium, dialkylammonium (C -C monium (C C alkoxyalkylammonium(C -C dialkoxyalkylammonium (C C aminoalkylammonium (C,Cdialkylaminoalkylammonium (C -C alkenylammonium (C -C alkyl (C -Caminoalkyl (C -C ammmonium, alkenyl (C2-C3o) aminoalkyl (C -C ammonium,alkynyl (C -C ammonium, dialkenylammonium (C C cycloalkylammonium (C -Calkyl (C -C ammonium alkyl (C -C ammonium, benzylammonium, anilinium,substituted anilinium, guanidinium or heterocyclicammonium (C Ctrialkylam- 12. The composition of claim 11, wherein said compound isbutylammonium 2-nitro-5-(2',4'-dichlorophenoxy) benzoate.

13. The composition of claim 11, wherein said compound ismethoxypropylammonium 2-nitro-5-(2',4'- dichlorophenoxy)benzoate.

14. The composition of claim 11, wherein said compound isdichlorophenoxy)benzoate cyclohexylammonium 2-nitro-5-(2',4- phenoxy)benzoate.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION QPATENT NO. 3,929A55 DATED December 30, 1975 |NVENTOR(5) ROBERT J.THEISSEN It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

Col. 3, line 39 "satuated" should be -satura.ted-.

Col. t, line 28 "33 2-pro oylammonium" should be -332-propynylammonium-- e Col. i, line 60 "65. n-dodecylamlno should be"65. n-dodecylamine-.

Col. line 65 "68. n-octadecyldimethylamino" should be -68.n-octadecyldimethylamine---.

Col. 5, line 22 "9o. momlpholine" should be -90. morpholine-.

Col. 8, Table 1 Example 37 under CN "01-" should be -O/- a H H Col, 8,Table 1 Example i9 under VL 50/1 should be Col. 12, line-9 "a-hltrol"should be -2-nitro-.

3 Col. 12, line 19 "2-nitro-5-nitro-5" should be 2nitro-5 Signed andSealed this [SEAL] ezghteenth Day Of May 1976 Arrest:

Q RUTH c. MASON -C. MARSHALL DANN ommissiunvr nflaleuls and TrademarksArresting Officer

1. THE METHOD FOR CONTROLLING PLANT GROWTH THAT COMPRISES APPLYING ANHERBICIDAL AMOUNT OF AN HERBICIDAL COMPOUND HAVING THE FORMULA:
 2. Themethod of claim 1, wherein said compound is butylammonium2-nitro-5-(2'',4''-dichlorophenoxy)benzoate.
 3. The method of claim 1,wherein said compound is methoxypropylammonium2-nitro-5-(2'',4''-dichlorophenoxy) benzoate.
 4. The method of claim 1,wherein said compound is cyclohexylammonium2-nitro-5-(2'',4''-dichlorophenoxy) benzoate.
 5. The method of claim 1,wherein said compound is 2,2-dimethoxyethylammonium2-nitro-5-(2'',4''-dichlorophenoxy)benzoate.
 6. The method of claim 1,wherein said compound is allylammonium2-nitro-5-(2'',4''-dichlorophenoxy)benzoate.
 7. The method of claim 1,wherein said compound is arachidyl (90%) behenyl (10%)aminopropylammonium 2-nitro-5-(2'',4''-dichlorophenoxy)benzoate.
 8. Themethod of claim 1, wherein said compound is potassium2-nitro-5-(2'',4''-dichlorophenoxy)benzoate.
 9. The method of claim 1,wherein said compund is ethanolammonium2-nitro-5-(2'',4'',6''-trichlorophenoxy) benzoate.
 10. The method ofclaim 1, wherein said compound is sodium2-nitro-5-(2'',4'',6''-trichlorophenoxy)benzoate.
 11. An herbicidalcomposition comprising a carrier for an herbicide and an herbicidalamount of an herbicidal compound having the formula:
 12. The compositionof claim 11, wherein said compound is butylammonium2-nitro-5-(2'',4''-dichlorophenoxy) benzoate.
 13. The composition ofclaim 11, wherein said compound is methoxypropylammonium2-nitro-5-(2'',4''-dichlorophenoxy)benzoate.
 14. The composition ofclaim 11, wherein said compound is cyclohexylammonium2-nitro-5-(2'',4''-dichlorophenoxy)benzoate
 15. The composition of claim11, wherein said compound is 2,2-dimethoxyethylammonium2-nitro-5-(2'',4''-dichlorophenoxy)benzoate.
 16. The composition ofclaim 11, wherein said compound is allylammonium2-nitro-5-(2'',4''-dichlorophenoxy) benzoate.
 17. The composition ofclaim 11, wherein said compound is arachidyl (90% ) behenyl (10%)aminopropylammonium 2-nitrol-5-(2'',4''-dichlorophenxoy benzoate. 18.The composition of claim 11, wherein said compound is potassium2-nitro-5-(2'',4''-dichlorophenoxy) benzoate.
 19. The composition ofclaim 11, wherein said compound is ethanolammonium2-nitro-5-(2'',4'',6''-trichlorophenoxy)benzoate.
 20. The composition ofclaim 11, wherein saiD compound is sodium2-nitro-5-nitro-5-(2'',4'',6''-trichlorophenoxy) benzoate.